Method for manufacturing semiconductor device

ABSTRACT

A method for manufacturing a semiconductor device comprises: immersing a semiconductor substrates in a Pd activating solution containing Pd ions and adhering a Pd catalyst to a surface of the semiconductor substrate; and immersing the semiconductor substrate, to which the Pd catalyst is adhered, in a Pd electroless plating solution and forming an electroless-plated Pd film on the semiconductor substrate.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for manufacturing asemiconductor device that can form the metal film having high coatingcharacteristics and adhesion on the semiconductor substrate at lowcosts.

2. Background Art

When electrodes other than an ohmic electrode are formed on asemiconductor substrate, generally, two layers or more metal films areoften formed using vapor deposition, sputtering or the like. For theupper layer, a material having high electric conductivity, whose surfaceis hard to be oxidized, such as Au, is used. In place of Au, Ag, Cu orthe like may be used. The lower layer is a barrier layer that preventsthe diffusion of Au into the semiconductor substrate. As the barrierlayer, Ti, TiN, TaN, Pt or the like is often used. Furthermore, in orderto secure required current, these layers may be subjected to Auelectrolytic plating as power supply layers. In place of Au electrolyticplating, Ag or Cu having high conductivities may also be used.

As the characteristics of the electrode, in addition to electricalcharacteristics, such as low electric resistance and electro-migrationsuppression, a sufficient adhesion is required for preventing peel-offduring die bonding or wire bonding. Therefore, as the metal for theelectrode contacting the surface of the semiconductor, a metal having ahigh adhesion to the semiconductor is used. For example, Ti or Pt isused for GaAs.

In addition, when a penetrating electrode that electrically connects thetop surface side to the back surface side of the substrate is formed inthe via hole that penetrates through the semiconductor substrate, theinner wall of the via hole must be sufficiently coated with a metalfilm. When the metal film is formed using vapor deposition orsputtering, the metal film on the sidewall of the via hole becomesthinner than the metal film on other portions. Therefore, the efficiencyof forming the metal film on the sidewall of the via hole is elevatedusing inverse sputtering or planetary vapor deposition.

SUMMARY OF THE INVENTION

However, by conventional methods using vapor deposition or sputtering,the thickness of the metal film on the sidewall of the via hole wasseveral percent the thickness on flat portions. Therefore, the loweringof yield due to poor conduction caused problems. Also in the case ofperforming Au electrolytic plating using the metal film formed by vapordeposition or sputtering as the power supply layer, the Au-plated filmwas not grown or abnormally grown in the via hole causing poorconduction or poor appearance, and also causing lower yield.

In view of the above-described problems, an object of the presentinvention is to provide a method for manufacturing a semiconductordevice that can form the metal film having high coating characteristicsand adhesion on the semiconductor substrate at low costs.

According to the present invention, a method for manufacturing asemiconductor device comprises: immersing a semiconductor substrates ina Pd activating solution containing Pd ions so as to adhere a Pdcatalyst on a surface of the semiconductor substrate; and immersing thesemiconductor substrate, on which the Pd catalyst is adhered, in a Pdelectroless plating solution so as to form an electroless-plated Pd filmon the semiconductor substrate.

The present invention makes it possible to form the metal film havinghigh coating characteristics and adhesion on the semiconductor substrateat low costs.

Other and further objects, features and advantages of the invention willappear more fully from the following description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 to 3 are sectional views for showing that a Pd-plated film isformed on the material to be plated other than group-VIII metals.

FIGS. 4 to 12 are sectional views for illustrating the method formanufacturing a semiconductor device according to the first embodiment.

FIG. 13 is a sectional view for illustrating the method formanufacturing a semiconductor device according to the comparativeembodiment.

FIG. 14 is a diagram showing the result of depth Auger analysis carriedout for the electroless-plated Pd film on the GaAs substrate.

FIG. 15 is a graph showing the stress to Pd-plated films by annealingtemperatures.

FIG. 16 is a top view for illustrating the method for manufacturing thesemiconductor device according to the second embodiment.

FIG. 17 is a sectional view for illustrating the method formanufacturing the semiconductor device according to the secondembodiment.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Heretofore, electroless plating of Pd onto a smooth surface, such as thesurface of a semiconductor substrate, was considered to be difficult.Theoretically, an electroless-plated Pd film can be formed on agroup-VIII metal, such as Pd and Ni, having a function to oxidize areductant on the surface to be plated. On the other hand, when aPd-plated film is formed on the material to be plated other thangroup-VIII metals, as shown in FIG. 1, after forming a thin film of thePd catalyst 12 on the surface of the material to be plated 10, platingis performed.

However, since the Pd catalyst 12 is merely adhered onto the surface,adhesion is poor. Therefore, as shown in FIG. 2, the Pd-plated film 14cannot be grown, may float, or easily peeled off. In general, in orderto compensate the weakness of adhesion, as shown in FIG. 3, the surfaceto be plated is roughened by blasting or the like to hold the Pdcatalyst 12 by the anchoring effect. However, since the surface of thesemiconductor substrate was basically made to be a mirror surface havinga surface roughness of Ra=1 nm or the like by a polishing process, thePd catalyst was considered not to be adhered.

This time, the present inventors found that an electroless-plated Pdfilm could be formed on a semiconductor substrate. The present inventorsconsider that the reason why the electroless-plated Pd film can beformed is because the Pd catalyst reacts with the semiconductorsubstrate. This will be described using a GaAs substrate as an example.It has been known that GaAs reacts with Pd to produce aPdGa_(−0.3)As_(−0.2) ternary eutectic at 20° C. to 250° C. (For example,refer to T. S. Kuan, J. Appl. Phys., 58 (4), 1985). Specifically, by aPd activating process (normally performed at 20° C. to 30° C.), afterthe Pd catalyst is adhered on the surface of the GaAs substrate, thePdGa_(−0.3)As_(−0.2) ternary eutectic is formed by the reaction withGaAs. Therefore, a favorable Pd layer can be formed even on a smoothsurface. Thus, the Pd-plated film can be stably formed by a Pdelectroless plating process in the subsequent step. Favorable adheringperformance can also obtained from the time of film forming.

On the basis of these findings, the present inventors devised thepresent invention. The embodiments of the present invention will bedescribed below referring to the drawings. The identical orcorresponding constitutes will be denoted by the same numerals, and therepetition of the description thereof will be omitted.

FIRST EMBODIMENT

A method for manufacturing a semiconductor device according to the firstembodiment of the present invention will be described. FIGS. 4 to 12 aresectional views for illustrating the method for manufacturing asemiconductor device according to the first embodiment.

First, as shown in FIG. 4, devices, such as an electrode 18 and atransistor (not shown) are formed on the upper surface of a GaAssubstrate 16 (semiconductor substrate). Then, as shown in FIG. 5, thedevice forming surface (upper surface) of the GaAs substrate 16 isadhered to a sapphire support substrate 22 having a thickness of about 1mm by an adhesive 20, such as wax and an adhesive tape. In such a state,the back surface of the GaAs substrate 16 is polished to thin the GaAssubstrate 16.

Next, as shown in FIG. 6, the GaAs substrate 16 is etched from the backsurface side. Thereby, a via hole 24 is formed through the GaAssubstrate 16 from the back surface of the GaAs substrate 16 to the backsurface of the electrode 18.

Next, as shown in FIG. 7, a plurality of GaAs substrates 16 in the stateof wafers are held in a cassette 26 so as not to contact with oneanother. In this state, the GaAs substrates 16 are immersed in a Pdactivating solution 28 containing Pd ions (Pd activating process). Theimmersing time is 1 to 5 minutes. Thereby, as shown in FIG. 8, which isan enlarged diagram, a Pd catalyst 30 having a thickness of severalnanometers is adhered on the surface of each GaAs substrate 16. Byelevating the temperature of the Pd electroless plating solution to 20°C. or higher, the Pd catalyst 30 reacts with the GaAs substrates 16 toform a Pd—Ga—As mixed layer 40.

Here, the Pd activating solution 28 is, for example, a palladiumchloride (PdCl₂) solution. The Pd content of the Pd activating solution28 is about 0.1 to 1.0 g/L. The Pd activating solution 28 is warmed to aliquid temperature of about 20 to 30° C. by a heater 32, and stirred bya stirrer 34. However, the adhering quantity or the uniformity of the Pdcatalyst 30 differs depending on the Pd content and/or liquidtemperature, causing the abnormality of interfacial adhesion, surfacemorphology, and film floating. Therefore, the Pd content and liquidtemperature must be adjusted within proper ranges.

When the surface wettability of the GaAs substrate 16 is poor, thepretreatment such as oxygen ashing and ozone ashing is carried outbefore performing the Pd activating process. Furthermore, surfaces maybe cleaned with an acid or alkali solution having the effect of removingthe surface oxide film to enhancing the adhesion of the solder film andthe semiconductor.

In addition, to inhibit film formation on the device itself, thecassette 26, the stirrer 34, and the handle 36 are made of Teflon® (DuPont™, USA). The beaker 38 is composed of Pyrex glass® (quartz), whichhas a high heat resistance and is hard to form a film on itself.

Next, as shown in FIG. 9, the GaAs substrate 16 on which a Pd catalyst30 is adhered is immersed in a Pd electroless plating solution 42.Thereby, as shown in FIG. 10 (enlarged diagram) and FIG. 11, a Pd-platedfilm 44 is formed on the GaAs substrate 16. Then, as shown in FIG. 12,an Au layer 46 is formed using Au electrolytic plating. Thereafter,annealing if performed, and the GaAs substrate 16 is peeled from thesapphire support substrate 22.

Here, the Pd electroless plating solution 42 is a solution containinghypophosphorous acid, which is a reducing agent; an inorganic acid salt,such as a chloride; ethylenediamine, which is an additive; and apalladium compound. Thereby, hypophosphite ions are oxidized using theadhered Pd catalyst 30 as the catalyst, the Pd ions are reduced by theelectrons released at this time, and the Pd-plated films 44 are formed.Specifically, the Pd-plated films 44 are formed on the back surface ofthe GaAs substrate 16, the sides of the via hole 24, and the backsurface of the electrode 18.

The Pd content of the Pd electroless plating solution 42 is about 0.1 to10 g/L. The Pd electroless plating solution 42 is heated by the heater32, and is used at a liquid temperature of about 50° C. To stablyperform plating, the bath volume of the Pd activating solution 28 andthe Pd electroless plating solution 42 is preferably at least 1 L for1.0 dm² of the plating area.

By performing annealing at 20° C. or above, Pd reacts with the GaAssubstrate 16, and a Pd—Ga—As mixed layer is formed. Specifically, whenthe annealing temperature is 20° C. to 250° C., a Pd—Ga—As ternaryeutectic is formed. When the annealing temperature is 250° C. to 350°C., a mixed crystal of PdAs₂ and Pd₂Ga is formed. When the annealingtemperature is 350° C. to 500° C., a mixed crystal of PdAs₂, Pd₂Ga, andPdGa is formed. Thus, the crystalline state is varied depending on theannealing temperature.

The effect of the present embodiment will be described comparing with acomparative embodiment. FIG. 13 is a sectional view for illustrating themethod for manufacturing a semiconductor device according to thecomparative embodiment. In the comparative embodiment, a Ti layer 48 andan Au layer 50 are sequentially formed on the surface of a GaAssubstrate 16 by vapor deposition or sputtering, and an Au layer 52 isformed thereon by electrolytic plating.

However, since the Ti layer 48 and the Au layer 50 on the sidewall ofthe via hole 24 are thinned, defective conduction occurs. Furthermore,when electrolytic plating is performed using the Ti layer 48 and the Aulayer 50 as power supply layers, the Au layer 52 is not grown orabnormally grown in the via hole 24.

In the present embodiment, on the other hand, the Pd-plated film 44 isformed on the GaAs substrate 16 after the Pd catalyst 30 has beenadhered on the surface of the GaAs substrate 16 by the Pd activatingprocess. Thereby, the metal film can be more uniformly formed on thesidewall of the via hole 24 comparing with sputtering or vapordeposition in conventional methods, and electrical conduction can beeasily secured. In addition, when the electrolytic-plating of Au isperformed, since the inner wall of the via hole is sufficiently coatedwith the Pd film, the abnormality such as non-growing of theelectrolytic-plated Au layer is hard to occur. Therefore, the metal filmhaving high coating characteristics and adhesion can be formed on thesemiconductor substrate at low costs.

FIG. 14 is a diagram showing the result of depth Auger analysis carriedout for the electroless-plated Pd film on the GaAs substrate. At thistime, the sample was annealed at 250° C. for 4 hours in a nitrogenatmosphere. As a result of the analysis, the same degrees of Pd, Ga, andAs were mixed in the depth direction. A tape test for adhesivecharacteristics (JIS Standard H-8514) was carried out, and the favorableadhesive characteristics of “no peel-off” were confirmed. It isconsidered that the adhesive characteristics were improved by theformation of the mixed layer.

FIG. 15 is a graph showing the stress to Pd-plated films by annealingtemperatures. The stress was lowered as the annealing temperature waselevated, and the stress was reduced to approximately half afterannealing of 320° C./1 hr comparing with after annealing of 100° C./10min. When stress is elevated, the wafer or chip is warped, and heatresistance characteristics or the like are deteriorated.

When the annealing temperature is determined, for example, the annealingtemperature is preferably 350° C. or lower, because if the GaAssemiconductor device is heated to 350° C. or higher, the characteristicsof the ohmic electrode and the active region are varied. On the otherhand, when resin die bonding is carried out at 250° C., it is preferableto previously perform annealing so as not to cause the variation ofstress characteristics during die bonding. In this case, annealing ispreferably performed at about 250° C. to 350° C. If die bonding isperformed using an AuSn solder (20% Sn), there is a thermal history ofabout 300° C. or higher. In this case, annealing is preferably performedat about 300° C. to 350° C.

Since Pd is not grown on the resist of an organic material or the like,an optional shape of the Pd film can be formed when electroless platingof Pd is carried out after the resist pattern has been formed on thesemiconductor substrate. After forming the plated film, the resist isremoved by organic cleaning.

Depending on the use of the electrode, other electroless-plated films,such as Ni, Cu, and Au films, may be formed on the electroless-plated Pdfilm. When all the patterns are connected, electrolytic plated films,such as Au, Ag, and Cu films, may be continuously formed.

SECOND EMBODIMENT

A method for manufacturing a semiconductor device according to thesecond embodiment will be described referring to the drawings. FIG. 16is a top view for illustrating the method for manufacturing thesemiconductor device according to the second embodiment; and FIG. 17 isa sectional view thereof.

First, a bump 54 is formed on a GaAs substrate 16 (semiconductorsubstrate) by etching. Next, in the same manner as in the firstembodiment, a Pd-plated film 44 is formed on the flat portion and theside portion of the bump 54 on the GaAs substrate 16. Thus, a Pd filmcan be uniformly formed on the surface of the semiconductor substratehaving the dump. For example, wirings or electrode pads across the bumpcan be formed without disconnecting or narrowing.

Obviously many modifications and variations of the present invention arepossible in the light of the above teachings. It is therefore to beunderstood that within the scope of the appended claims the inventionmay be practiced otherwise than as specifically described.

The entire disclosure of a Japanese Patent Application No. 2010-025464,filed on Feb. 8, 2010 including specification, claims, drawings andsummary, on which the Convention priority of the present application isbased, are incorporated herein by reference in its entirety.

1. A method for manufacturing a semiconductor device comprising:immersing a semiconductor substrate in a Pd activating solutioncontaining Pd ions thereby adhering a Pd catalyst to a surface of thesemiconductor substrate; and immersing the semiconductor substrate, towhich the Pd catalyst is adhered, in a Pd electroless plating solutionand forming an electroless-plated Pd film on the semiconductorsubstrate.
 2. The method for manufacturing a semiconductor deviceaccording to claim 1, wherein the semiconductor substrate is GaAs. 3.The method for manufacturing a semiconductor device according to claim1, wherein the Pd activating solution is a palladium chloride solution.4. The method for manufacturing a semiconductor device according toclaim 1, wherein, in forming the electroless-plated Pd film, maintainingthe temperature of the Pd electroless plating solution at 20° C. orhigher.
 5. The method for manufacturing a semiconductor device accordingto claim 1, further comprising annealing the electroless-plated Pd filmat a temperature in a range from 250° C. to 350° C.
 6. The method formanufacturing a semiconductor device according to claim 5, includingannealing at a temperature in a range from 300° C. to 350° C.
 7. Themethod for manufacturing a semiconductor device according to claim 1,further comprising: forming an electrode on an upper surface of thesemiconductor substrate; forming a via hole through the semiconductorsubstrate from a back surface of the semiconductor substrate to a backsurface of the electrode; and forming the electroless-plated Pd film onthe back surface of the semiconductor substrate, a side surface of thevia hole, and the back surface of the electrode.
 8. The method formanufacturing a semiconductor device according to claim 1, furthercomprising: forming a bump having a flat portion and a side portion onthe semiconductor substrate; and forming the electroless-plated Pd filmon the flat portion and the side portion of the bump.